Manufacture of salts of alkyl acid sulfates in one step



United States Patent MANUFACTURE OF SAUTS 0F ALKYL ACID SULFATES-IN0NE-STEP movers c. Harrington, 1nngspon, Tenn assignma 5 craters. ((El.260 2471) -Thisinvention 1 relates to "therpreparation' "of substitutedainmonium salts of sulfated-alcohols. More particularly it relates tothe manufacture in one step of such sulfated alcohol salts.

Sulfation or'sulfonation or the like treatment of various organiccompounds including 'lohg 'cliainalcohols is well known procedure in'theindustry=as described in various texts such as Unit Pi'ocesses inOrganic Synthesis, Groggins, 1938. Also other publications such as:Industrial st-En ineerin Chemistry for September l9'5'4,"dscribe "anlimbrof sulfating'prodesses.

Sulfat'ionin general is accomplished'wi'th surge number of sulfatin'g*ag'e'nts, "predominant "among which are sulfuric-acid, fuming sulfuricacid, chlorosulfonic acid, sulfar'nidacidand pyridine-sulfu'r ti ioxidecomplexes. In prior art 'rn'ethods of "sulfat'ing alcoholsiwith theseinaterials, problems such as the formationof color and the attack ondouble bonds in "the 'fatty alcohol molecule have been encountered.While some of the-priorgart processes a'n'd 'sulfating agents willaccomplish one aim, they may fail drastically 'at' some other point. Ingeneral in the prior art procedures after sulfation with sulfatingagents of the aforementioned type, the sulfated fatty alcohol must beneutralized with ammonia, sodium or potassium hydroxide or the like,which maytpresent further problems.

2,849,450 l atented Aug. 2c, 1958 extentcan occur. Hence, the presentinvention which provid s a simpler and improved process of mak- 115gsuch products; as well as the production of a better typ isnsauet, isbelieved to possess particular merit.

This invention has for one object to provide an improved procedureproducing substituted amine or aminoniuin salts of sulfat'ed alcohols.Still another object is to provide a substai tially one-step method ofproducing compounds of the class aforesaid. An additional object is-t5provide a new process of sulfation which may be applied to unsaturatedalcohols without material danger of sulfation of the ol'efi'n'ic doublebond. A still further object of this invention is to produce substitutedammonium salts of sulfated alcohols characterized by. being light incolor. Another object is to provide asimplified;

improved process for producing salts of sulfated alcohols In furtherdetail, in most prior art sulfation methods it is difficult to sulfatematerials containing an olefinic double bond, such as oleyl alcohol,without sulfating across this double bond. When suehreactiontakes place,a compound is for-med having inuch lower surface active characteristicsthan when only the alcohol group is sulfated. -Furt-hrmorejin generalsiilfation reactions in accordan'ce with the priorart, a certain amountof'd radationmay takeeplaee and thereaction mixture may develop an'undesirabl'edark color. 'Also, *the problemof neutralizing "s'u'lfat'ed"alcohols as -ni'en't io'nedfabove must be resolved, and while this canbe donefin "accordance yiiith prior art procedures "with a reasonableamount of equipment, it does represent a second step and adds toexpense. However, there is an especially troublesome problem if hightemperatures are created during neutralization, since alkyl sulfatestend to decompose when heated in the acidic state.

It is therefore apparent that the development of an improved processwhereby the aforementioned type of difiiculties may be eliminated orininiiiiized' represents a highly desirable result. Not only are certainprocess advantages obtained by iny one-step type of method which will bedescribedin detail hereinafter, but added -ad'- vantages may be obtainedin the production, in many instances, of a better colored product. Thatis, it is apparent in some instances, in the use of such s'alt's, as forexample in the treatment of yarns with textile treating agentscontaining salts of the -'aforei'nentioned type by old methods ofmanufacture and which may not be of good color characteristics, thatpossibly damage to the yarn to of the class indicated which are suitablefor use as surface active agents, detergents, Wetting agents, componentsof yarn treating compositions and the like. Other objects will appearhereinafter;

In the broader aspects of my invention I have found that organiccompounds to be converted to substituted ammonium salts of alkyl acidsulfates, such as long chain alcohols exemplified by oleyl alcohol,lauryl alcohol and the like, may have added thereto an amine beforesulfating, or, as will be described in connection with certainvariations of my invention, the amine or certain other agents may beadded tothe -'sulfating material prior to the one-step reaction with thealcohol to be sulfated. In either instance this invention gives a methodof sulfating alongwith salt formation at the same time. In other words,I have found an efiicient one-step process from the fatty alcohol to theformation of the salt of the sul= fated al'cohol. By thus producing thesalt in one step, the color produced; during the typical 'prior artsulfation reaction is usually bypassed and in most instances lightercolored products are thus obtained. The one-step method in accordancewith the present invention makes possible the sulfation of olefinicalcohols without the deleterious attack at the double Bond.

' nte "equipment required for this invention is relatively 'sin'iple,consisting only of an op'en neared kettle equipi'nn't with a stirrer.The controls are also very simple, flsirtlfermo there is no problem ofthe prior art type concerning l en't reriiov al 'orfinal neutralization.That is, in i entioh at the end of the one reaction the final r use isobtained.

4 r aspects of my process may be considered under two headings,depending on whether the compound i's p'recombincd the alcohol orwhether the compound is precombined with the sulfating medium.

(A) In accordance with the reaction under this heading, the alcohol tobe processed in accordance with the present invention, =is premixedwith, for example, an alkylol amine. Considering '1aur'yl alcohol as thelong chain a1- cohol desired treated, the lauryl alcohol is mixed with achemical such as an amino alkyl propanol, with stirring. Thereafter themixture 'of the alcohol and amine is subjected to treatment with a"sulfating agent under certain conditions which will be described indetail hereinafter. In general I prefer in several respects to employthe procedure-justdescri-bed. However, certain al'terna'tive procedures-may be carried out as will be briefly mentioned in-thenext paragraph.

(B) In accordance with the procedure under this heading the amine may beadded to the 'sulfating' medium, such as to the sulfuric acid in acertain manner, and the resultantcotnbination then reacted with the longchain alcohol. Further details concerning this aspect of my inventionwill be -set' term in detail toward the endof the instant specification.

I have found by proceeding as just briefly indicated, that asubstantially one-step process can be accomplished and that in additionto improved operation there may also be obtained an improved product.That is, products produced by my one-step process in many instances arelighter colored than conventionally produced products. Accordingly, mylighter colored products in many instances possess particular merit andutility in formulating compositions for use in treating textiles.

A more complete understanding of my invention will be had by referenceto the several examples which follow. These examples are set forthprimarily for illustrating certain preferred embodiments of myinvention. In Examples I through VIII the reference to oleyl means ahydrocarbon chain of the following formula:

CH (CH CH= CH (CH CH In Examples IX through XV the reference to laurylmeans a hydrocarbon chain having the following formula:

Example I This example describes the preparation ofN-(1,1-dimethyl-Z-hydroxy ethyl) ammonium oleyl sulfate having theformula:

One mole (89 grams) of Z-amino-Z-methyl-l-propanol is mixed with onemole (268 grams) of oleyl alcohol. This mixture is agitated and to it isadded one mole (98 grams) of concentrated sulfuric acid at such a ratethat the temperature of the reaction mass reaches 110 C. When thetemperature begins to drop it is maintained at about 100 C. for 4 hours.A reasonably light colored material having high emulsification powersand having a degree of sulfation of 68% was obtained by this procedure.

Example II This example also describes the preparation of N-(1,1-dimethyl-2-hydroxy ethyl) ammonium oleyl sulfate but using lowertemperatures. One mole (89 grams) of 2- amino-2-methyl-l-propanol ismixed with one mole (268 grams) of oleyl alcohol (commercial Ocenol).One mole (98 grams) of concentrated sulfuric acid is added to themixture with strong agitation. The temperature is allowed to reach 100C. during this addition and is maintained at 100 C. for 1% hours. Thetemperature is then lowered to 90 C. for 6 hours at which time theproduct is recovered as a brown viscous liquid which by analysis isshown to be about 55% sulfated.

Example 111 This example describes the preparation of the morpholinesalt of oleyl sulfate, having the formula:

One mole (87 grams) of morpholine is mixed with one mole (268 grams) ofoleyl alcohol. To this is added one mole (98 grams) of concentratedsulfuric acid while the whole reaction mass is vigorously agitated. Thetemperature is allowed to go to 110 C. during this step and ismaintained thereafter at 100 C. for 7 /2 hours. The product obtainedfrom this reaction solidifies to a light solid showing a degree ofsulfation of 68%. This N-morpholine oleyl sulfate has very goodemulsifying powers.

.4, Example IV This example describes the preparation of pyridine oleylsulfate having the formula:

One mole (79 grams) of pyridine is mixed with one mole (268 grams) ofoleyl alcohol. This mixture is vigorously stirred and to it is added onemole (98 grams) concentrated sulfuric acid. The temperature reachesabout 92 C. during the addition and is thereafter maintained at 100 C.for 7 hours. At the end of this time the reaction product solidifies toa light solid which shows good emulsifying powers and is 73% sulfated.

Example V This example describes the preparation of N-(l-ethyl-2-hydroxy ethyl)ammonium oleyl sulfate, having the formula:

One mole (268 grams) of oleyl alcohol is mixed with one mole (89 grams)of 2-amino-1-butanol. The mixture is well stirred and to it is added onemole (98 grams) of concentrated sulfuric acid at such a rate that thetemperature reaches 110 C. At the end of this addition the temperatureis maintained at 100 C. for 7 /2 hours. The reaction product is a liquidand shows good emulsifying properties.

Example VI This example describes the preparation of N-(1,1-bis hydroxymethyl propyl)ammonium oleyl sulfate having the formula:

This example describes the preparation of N-phenyl- N-hydroxy ethylammonium oleyl sulfate having the CHzCHzOH One mole (268 grams) of oleylalcohol is mixed with one mole (133 grams) of phenyl ethanolamine. Onemole (98 grams) of concentrated sulfuric acid is added with agitation tothis mixture and the temperature allowed to reach C. At the end of thistime the temperature is adjusted to C. for 7 hours. The productcollected from this reaction is a gray solid showing good emulsifyingcharacteristics.

kept there for 7 hours.

Example VIII This example describes the preparation of pyrrolidin- -iumoleyl sulfate having the formula:

CHrOHz CHr-CHz -One mole (268 grams) of oleyl alcohol is mixed with onemole (71 grams) of pyrrolidine. This mixture is Well agitated and onemole (98 grams) of concentrated sulfuric acid added at such a rate thatthe temperature reaches 110 C. After the addition of the sulfuric acidis complete the temperature is adjusted to 100 C. and The productobtained from this reaction is a liquid showing good emulsifyingproperties.

Example IX This example describes the preparation ofN-(l,1-dimethyl-Z-hydroxy ethyDammonium lauryl sulfate having theformula:

One mole (186 grams) of lauryl alcohol is mixed with one mole (89 grams)of 2-amino-2-methyl-1-propanol. To this well stirred mixture is addedone mole (98 grams) of concentrated sulfuric .acid. The addition of thesulfuric acid is adjusted to give a temperature rise up to 120 'C. Atthe end of this time the temperature is adjusted to 100 C. and keptthere for 7 /2 hours. The product resulting from-this reaction is awhitesolid having good emulsifying properties and showing a degree ofsulfation of 58%.

Example X This example describes the preparation of N-(bis'hydroxyethyl)ammonium lauryl sulfate, having the formula:

i-Ha 'b-bOH Lauryl-O-S-OH-H c-oon One mole (186 grams) of lauryl alcoholis mixed with onemole (105 grams) ofdiethanolamine. This mixture is wellagitated while one mole (98 grams) of concentrated sulfuric acid isaddedat such a rate that the temperature reaches 120 C. After theaddition is complete the temperature is adjusted to 100 C. and keptthere for 7 /2 hours. The product thus obtained shows fair emulsifyingproperties.

Example XI This example describes the preparation of N-mor- .pholyllauryl sulfate, having the formula:

One mole (186 grams) of lauryl alcoholis mixed with one mole (87 grams)of morpholine. This mixture is well stirred and to it is added one mole(98 grams) of concentrated sulfuric acid. The temperature is allowed togo to 130 C. during the addition ofacid and is'later adjusted at 100 C.for 7 /2 hours. A very=clear, light colored material is obtained whichhas very good emulsi- "fying powers and shows a degree ofsulfation of78%.

6 Example XII I This example describes the preparationof N-methyl*morpholine salt of lauryl sulfate having the formula:

'O'ne-mo1e'(1 86 grams) of lauryl alcohol is mixedw'ith one mole-(101grams) of N-methyl morpholine. This mixture is stirred vigorously and toit'is 'added one male (98 grams) of concentrated sulfuric acid at'sucha'rate that the temperature rises to 120C. When all of the acid isadded the temperature is'maintained at 120 C. for 7 /2 hours. Theresulting "product is a light'tan'soli'd showing good emulsifying"characteristics and showing a degree of sulfation of 73%.

Example- XIII This example describes the preparation of the pyridinesalt of lauryl sulfate, having theformula:

One mole (79 grams) of pyridine is added with vigorous stirring to onemole (186 grams) of laurylalcohol.

Thenone mole (98 grams) of concentrated sulfuric "acid is addedgradually so "that the temperature rises to 120 C. The temperature isthen settledat C.-f0r '6 hours. At the end of this time a product isobtained whichisa'white solid andhas a degree of sulfation of 68%. "Thismaterial also shows high emulsifying characteristics.

Example -XI V V This example describes the preparation of the N,N-'dimethylamino ethanol salt of lauryl sulfate having the formula:

. This example describes the preparation of N-( l-ethyL2-hydroxyethyl)ammonium lauryl sulfate having the formula:

11 "Lauryl-O|S--0H-H2N( JHa- CHzOH One mole (89 grams) of2-amino-1-butanol is added to one mole (186 grams) of lauryl alcohol.This mixture is vigorously agitated while one mole (98 grams) ofconcentrated sulfuric acid is added at such a rate that the temperaturereaches 122 C. The temperature is then adjusted to 100 C. and kept therefor 7 /2 hours. At the end of this time a very light colored viscousliquid was obtained as the product and it showed good emulsifyingcharacteristics along with a degree of sulfation of 65%.

yield and having a good color.

Description will now be set forth relative to carrying out my inventionin accordance with modification B.

referred to earlier in the specification. It will be recalled that inaccordance with this modification the alkylol amine or the like compoundis premixed in a certain mannet with the sulfating medium. The productobtained is then used to react with the alcohol thereby producing asubstituted ammonium salt of a sulfated alcohol in good It is alreadyindicated above that this feature of premixing of the present inventionpermits the treatment of unsaturated fatty alcohols without obtaining areaction at the double bond.

The sulfating agents obtained by the premixing in accordance with partB. of the present invention are de scribed by the following formula:

( (R') (R) NHSO OH R is 2 2 HOCH C(CH CHr-CH:

CHPCfifl In (a) and (b), R can be (d) CH (e) CH CH or (f) In (d) and(e), R" isH In (c), R is H, and there is no R".

These sulfating agents are easily prepared by dissolving one mole of thealkylolamine, for instance, in an inert solvent such as ether or carbontetrachloride (many different chlorinated hydrocarbons and ethers willdo as well). To this rapidly stirred mixture, one mole of concentratedsulfuric acid is added and the resulting precipitate collected. Thisprecipitate, the alkylolamine sulfate, is freed from inert solvent, andmixed in molar proportions with the fatty alcohol. This mixture is wellagitated and heated over a period of 2 to 7 hours. At the end of thistime, the alkylol substituted ammonium fatty alcohol sulfate iscollected and is ready for use as a detergent or emulsifying agent, forexample. This reaction is described by the following equation:

100 C. (R)(R')(R")NHSO3OH R'OH R'OSO2ONH(R)(B')(R") R, is C10 t C20- Amore specific example follows:

CH3 HOCHr--NHaSOqOH OH3(OHz)1oCHz H CH3 CH3(CHz)mCHzOSOzONHr-CHzOH Theutilization of modified sulfating agents as just described above will befurther apparent from the following specific examples:

Example XVI Preparation of N-(1,l-dimethyl-Z-hydroxyethyl) ammoniumlauryl sulfate. One mole of N-(1,1-dimethyl-2- hydroxyethyl) ammoniumsulfate was prepared by adding one mole of concentrated sulfuric acid toa solution of 1 mole of 2-amino-2-methyl-l-propanol in ether. Theresulting white, crystalline solid was collected and added to 1 mole(186 grams) of lauryl alcohol. This mixture was well stirred and heatedto 135 C. for 2 hours. A light colored material of high surface activitywas obtained from this reaction.

Example XVII Preparation of N-(1,1-dimethyl-2-hydroxyethyl) ammoniumoleyl sulfate. One mole of N-(1,1-dimethyl-2- hydroxyethyl) ammoniumsulfate was prepared in the manner described in Example XVI, and addedto 1 mole 8 (268 grams) of oleyl alcohol. The mixture was stirred andheated at C. for 8 hours. At the end of this time, a light amber coloredmaterial having good surface active properties was collected.

Example XVIII Preparation of morpholinium lauryl sulfate. One mole ofmorpholine sulfate was prepared by adding 1 mole (98 grams) ofconcentrated sulfuric acid to 1 mole (87 grams) of morpholine dissolvedin 1 liter of diethyl ether. The morpholine sulfate was collected andadded to 1 mole (186 grams) of lauryl alcohol. This mixture was heatedto C. for 5 hours along with vigorous stirring to give a light-colored,solid morpholine salt of sulfated lauryl alcohol. This material had goodemulsifying and surface active qualities.

It can be seen from the above description that we have provided arelatively simple, economical method of manufacturing substitutedammonium salts of alkyl acid sulfates. Our method is particularlybeneficial in enabling the production of such salt products,particularly sulfated alcohol salts, of excellent light color.

The temperature of the reaction may be from about 50 C. to 150 C. Whilein many instances it is preferred to incorporate the additive, such asthe alkylol amine, with the long chain alcohol to be treated, in someinstances as shown by certain of the examples, such type compound may beincorporated with the sulfating medium in a particular manner.

While my invention is particularly directed to the treatment of theillustrative alcohols oleyl and lauryl, certain aspects thereof may beapplied to other alcohols containing from 5 to 20 carbon atoms in thestraight or branched chain, examples of which are amyl, isoamyl, octyl,lauryl, octadecyl and the like. Likewise, alcohols containing more thanone primary hydroxyl group or a secondary hydroxyl group, exemplified bydecanediol- 1,10, may be similarly treated.

For further showing the utility of products produced in accordance withmy invention as above described, cellulose acetate yarn of 150 denier,38 filament, bright type was used in a test. This yarn was treated with1.0% of an alcohol sulfate salt produced generally in accordance withExample III. The yarn was subjected to the following treatment whichindicated that products produced in accordance with this inventionpossessed good yarn treating properties. A sample of this treated yarnwas placed in a test tube and heated at C. for a period of two hours.

The color of the treated yarn was examined contemporaneously with thetreatment and no noticeable change of color (darkening) was observedwhen examined under natural light. A sample of the same yarn treatedwith conventionally prepared alcohol sulfate of the same chemical type,was examined under the same conditions. A darkening of the yarn wasnoticeable, substantially immediately.

Observation of the yarn treated with the material of the presentinvention after a period of 90 days under "normal storage conditionsshowed no material darkening, thereby indicating that the improved colorobtainable was relatively stable.

While the products of the present invention which have improved colorare particularly useful in the textile trade, they may also be used forother purposes such as shampoo, household detergents and other washingand cleaning compounds.

I claim:

1. A process of manufacturing substituted ammonium salts of sulfatedlong chain alcohols wherein the alcohol chain is of 5-20 carbon atoms,the salts having good color and being produced in substantially one stepwhich comprises premixing said 5-20 carbon atom alcohol with a nitrogencontaining compound from the group consisting of alkylol amines andmorpholine, then-bringing the aforementioned premixture into reactivecontact with a sulfating agent from the group consisting of sulfuricacid and chlorosulfonic acid while agitating the aforesaid materials.

2. A process of manufacturing substituted ammonium salts of oleylalcohol in substantially one step which comprises premixing oleylalcohol with morpholine, then bringing the aforementioned premixtureinto reactive contact with a sulfating agent from the group consistingof sulfuric acid and chlorosulfonic acidwhile agitating the aforesaidmaterials.

3. A process of manufacturing substituted ammonium salts of oleylalcohol in substantially one step which comprises premixing oleylalcohol with an amino alkyl propanol, then bringing the aforementionedpremixture into reactive contact with a sulfating agent from the groupconsisting of sulfuric acid and chlorosulfonic acid while agitating theaforesaid materials.

4. The process in accordance with claim 1 wherein the alcohol is fromthe group consisting of oleyl and lauryl alcohols.

5. A process of manufacturing substituted ammonium salts of sulfatedlong chain alcohols wherein the alcohol chain is of 5-20 carbon atoms,the salts having good color and being produced in substantially one stepwhich comprises premixingsaid 5-20 carbon atom alcohol with a nitrogencontaining compound from the group consisting of alkylol amines andmorpholine, then bringing the aforementioned premixture into reactivecontact with a sulfating agent from the group consisting of sulfuricacid and chlorosulfonic acid while agitating the aforesaid materials,and maintaining the temperature of the reaction between 50150 C. for notmore than eight hours and thereafter isolating the salt prepared by theaforesaid process.

References Cited in the file of this patent UNITED STATES PATENTS646,772 Verley Apr. 3, 1900 2,147,811 Baldwin et a1. Feb. 21, 19392,256,877 Bertsch Sept. 23, 1941 2,537,868 Urban Jan. 9, 1951 2,553,993Wiest May 22, 1951

1. A PROCESS OF MANUFACTURING SUBSTITUTED AMMONIUM SALTS OF SULFATEDLONG CHAIN ALCOHOLS WHEREIN THE ALCOHOL CHAIN IS OF 5-20 CARBON ATOMS,THE SALTS HAVING GOOD COLOR AND BEING PRODUCED IN SUBSTANTIALLY ONE STEPWHICH COMPRISE PREMIXING SAID K-20 CARBON ATOM ALCOHOL WITH A NITROGENCONTAINING COMPOUND FROM THE GROUP CONSISTING OF ALKYLOL AMINES ANDMORPHOLINE, THEN BRINGING THE AFOREMENTIONED PREMIXTURE INTO REACTIVECONTACT WITH A SULFATING AGENT FROM THE GROUP CONSISTING OF SULFURICACID AND CHLOROSULFONIC ACID WHILE AGITING THE AFORESAID MATERIALS.